臺灣博碩士論文加值系統

過去四十年來，在台灣及日本發生許多起因過氧化丁酮火災所引發之熱爆炸事件，其衝擊在全世界化災史上佔主要的地位，因此其本質潛在危害值得進一步探討。首先以差示掃描熱卡計針對商業用之過氧化丁酮進行初步熱掃描，可獲得分解熱及放熱起始溫度。接著利用緊急排放安全處理儀進行更深入之失控現象研究。利用獲得之熱動力學數據及危害現象進行過氧化丁酮熱危害分析探討。
藉由差示掃描熱卡計研究結果發現，過氧化丁酮熱分解共有兩支放熱波峰，第一支波峰其反應級數為1級，活化能為Ea (kcalmol-1) = 25.9，頻率因子為lnA (s-1) = 27；第二支波峰其反應級數為0.3級，活化能為Ea (kcalmol-1) = 28.2，頻率因子為lnA (s-1) = 24。另外，利用緊急排放安全處理儀於絕熱狀態下所獲得之動力數據為，反應級數為1級，活化能為Ea (kcalmol-1) = 20.3，頻率因子為lnA (s-1)= 20.7。兩者的差別也做了相當的比較分析，希冀由本研究對其於受熱狀態下，主要產生之危害做一初步探討，以提供妥善的危害預防及處理方式，給予製程工廠做為設計及防範之依據。

In the past forty years in Japan and Taiwan, many thermal explosions have been caused by methyl ethyl ketone peroxide (MEKPO) under the influence of external fire. Thermograms of commercialized MEKPO with dimer were first screened by Differential Scanning Calorimetry (DSC) to determine the heat of decomposition and exothermic onset temperature. Thermal runaway phenomena were then thoroughly investigated by Vent Sizing Package2. (VSP2) Data of thermokinetics and thermal analysis were used for hazard evaluation of MEKPO thermal explosions.
Instead of normal one reaction peak from the adiabatic calorimeter, two exothermic peaks on the DSC thermograms is novel finding among literatures. It was found that the reaction order of 1st peak of MEKPO decomposition by isothermal analysis was 1. The Arrhenius parameters were calculated to be Ea (kcalmol-1) = 25.9 and lnA (s-1) = 27, with reproducible confirmation. The reaction order of the 2nd peak of MEKPO decomposition was 0.3 by DSC, showing the Arrhenius parameters of Ea (kcalmol-1) = 28.2 and lnA (s-1) = 24. By VSP2, the Arrhenius parameters were determined as lnA (s-1) = 20.7, Ea (kcalmol-1) = 20.3, and n = 1, respectively. Preventative measures can be established by these basic parameters so that the pro-active disaster prevention program can be practically reached.

中文摘要ii
英文摘要ii
誌謝 …iii
目錄 iv
表目錄 vi
圖目錄 vii
符號說明ix
第一章﹑緒論1
1.1 研究緣起1
1.2 研究目的2
1.3 研究內容2
1.4 預期成果4
第二章﹑文獻回顧5
2.1 過氧化丁酮熱危害分析5
2.2 過氧化丁酮管理、運輸相關規定7
第三章﹑過氧化物特性12
3.1 有機過氧化物特性12
3.2 有機過氧化物熱危害評估12
3.3 過氧化丁酮製程特性13
第四章﹑理論與應用18
4.1 n階反應測試理論18
4.2 絕熱昇溫測試理論19
4.3 熱動力參數應用技術20
第五章、實驗方法22
5.1 實驗設備22
5.2 儀器測試理論22
5.2.1 差示掃描熱卡計22
5.2.2 緊急排放安全處理儀25
5.3 操作流程26
5.3.1 差示掃描熱卡計實驗26
5.3.2 緊急排放安全處理儀實驗27
第六章、結果與討論35
6.1 DSC熱分析掃描35
6.1.1 DSC熱分析35
6.1.2 熱失控危害數據探討與分析37
6.2 VSP2絕熱失控反應40
6.2.1 絕熱失控危害40
6.2.2 絕熱失控危害數據探討與分析40
6.3 MEKPO Dimer動力參數計算46
6.3.1 第1只放熱波峰活化能與頻率因子之計算46
6.3.2 第1只放熱波峰反應速率常數之計算46
6.3.3 第2只放熱波峰活化能與頻率因子之計算46
6.3.4絕熱條件下活化能與頻率因子之計算47
6.4 MEKPO動力參數之探討50
第七章、結論與建議52
7.1 結論52
7.2 建議53
參考文獻54
附錄57
附錄一﹑MEKPO之DSC昇溫掃描熱譜圖58
附錄二﹑MEKPO之VSP2失控反應圖62
附錄三﹑EDUG研討會投稿70
自傳 87

1.王義文，1999，異丙苯過氧化氫不相容性之熱危害分析，國立雲林科技大學，碩士論文。
2. 行政院勞工委員會，“危害物及有害物通識規則”。
3. 侯宏誼，2000，異丙苯過氧化氫低溫放熱行為之研究，國立雲林科技大學，碩士論文。
4. 徐啟銘，王義文，杜逸興，1999，“有機過氧化物熱爆炸之防範與案例分析”，化工技術，頁122-134，1月。
5. 胡冠華、杜逸興、高振山、李全，1999，化學反應熱危害評估與反應技術手冊，工研院工安衛中心，新竹。
6. 施多喜，1980“有機過氧化物MEKPO及BPO之防災”，刑事科學，第29期，頁9-23。
7. 施多喜，1981“有過氧化物之理化性質”現代消防，第17卷，頁4-7。
8. 曹彰明，1996“有機過氧化物近年的發展”化工技術，第43卷，第4期，頁54-62。
9. 福山郁生，1992“有機過酸化物的事故例”，Explosion, 2 (2), 119.
10. 陳美玲，杜逸興，柏雅玲，1994，有機過氧化物之熱危害評估，工研院工安衛中心，新竹。
11. 黃河樺，1998，異丙苯過氧化氫熱危害分析與熱分解反應機制探討，國立雲林科技大學，碩士論文。
12. 張芳塻、黃振家，1996“爆炸物質危害事故之探討”，火藥技術，第12卷，第2期，頁65-83。
13. 楊毓中，2000，應用絕熱卡計於區分過氧化氫溶液在氯化氫之催化反應與自分解反應之研究，國立雲林科技大學，碩士論文。
14. 廖宏章、陳重仁、林永芬，1998，過氧化物熱爆炸危害消減系統，工研院工安衛中心，新竹。
15. 蕭保橞，1997“有機過氧化物之儲存與安全管理”，工業安全衛生月刊，第95卷，頁26-31，5月。
16. A Guide to the control of Industrial Major Accident Hazards Regulations, HES, 1984.
17. Akzo Nobel Chemicals, Inc. 1996, “Curing Agents for Thermoset Resins”, pp. 1-4.
18. Code for the Storage of Organic Peroxide Formulations, 1986, NFPA 43B, National Fire Protection Association, Quincy, MA, USA.
19. Duh, Y. S., Hsu, C. C., Kao, C. S., and Woeiyu, S., 1996, ”Applications of Reaction Calorimetry in Reaction Kinetics and Thermal Hazard Evaluation”, Thermochem. Acta, pp. 2899, 1-13.
20. Duh, Y. S., Kao, C. S., Lee, C. and Yu, S. W., 1997, “Runaway Hazard Assessment of Cumene Hyproperoxide form the Cumene Oxidation Process”, Trans. IchemE., Vol. 75, Part B, May pp. 73-80.
21. Duh, Y. S., Kao, C. S., Hwang, H. H. and Lee, W. L., 1998 “Thermal Decomposition Kinetics of Cumene Hydroperoxide”, Institution of Chemical Engineers, Vol. 76, pp. 271-276.
22. Fauske & Associates, Inc., 1996, VSP2 Manual and Methodology.
23. Fauske & Associates, Inc., 1985, “New Experimental Technique for Characterizing Runaway Chemical Reactions”, pp. 39-46.
24. Federal Register, Department of Transportation, Part Ⅱ, USA, 1990,Vol. 55, No. 246.
25. Fisher, H. G., and Goetz, D. D., 1991, “Determination of Self-accelerating Decomposition Temperatures using the Accelerating Rate Calorimeter”, J. Loss Prev. Process Ind., Vol. 4, pp. 305-316.
26. Frank, P. L., 1996 “Loss Prevention in the Process Industries: Hazard Identification, Assessment and Control, 2nd ed., Vol. 1-3.
27. Gustin, J. L., 1993, ”Thermal Stability Screening and Reaction Calorimetry. Application to Runaway Reaction Hazard Assessment and Process Safety Management”, J.Loss Prev. Process Ind., Vol. 6, pp. 275-291.
28. Hirose, Y., 1999 “Organic Peroxides as Curing Agents for Unsaturated Polyester Resins”, Kayaku Akzo Corporation, pp. 1-18.
29. John Barton and Richard Rogers, 1993, Chemical Reaction Hazards-A Guide, Published by Institution of Chemical Engineers, Davis Building.
30. Kossoy, A., Belochvostov, V. and Gustin, J. L. 1994 “Methodological Aspects of the Application of Adiabatic Calorimetry for Thermal Safety Investigation”, J. Loss Prev. Process Ind., Vol. 7, pp. 397-402.
31. Lee, P. R. 1969 “Safe Storage and Transportation of some Potentially Hazardous Materials” J. Appl. Chem., Vol. 19, pp. 345-351. December.
32. Mettler Toledo, 1998.STARe Software with Solaris Operating System, Operating Instructions.
33. Milas, N. A. and Golubovic, A., 1959 “Studies in Organic Peroxide. XXV. Preparation, Separation and Identification of Peroxides Derived from Methyl Ethyl Ketone and Hydrogen Peroxide”, J. Am. Chem. Soc., Vol. 81, pp. 5824-5826.
34. Mohan, V. K. et al., 1982, J. Haz. Mat., Vol. 5, pp. 197-220.
35. NFPA 43B, 1993 Storage of Organic Peroxide Formulations, National Fire Protection Association, Quincy, Massachusetts, USA.
36. OSHA, 1989 “Methyl Ethyl Ketone Peroxide Organic Method＃77”, 1-21.
37. “Safe Storage and Handling of Reactive Materials”, 1995, published by Center for Chemical Process Safety of the AIChE, New York, USA.
38. Shaw, D. H., and Pritchard, H. A., 1968, “Thermal Dcomposition of Di-tert-butyl Peroxide at high pressure”, Can J Chem., Vol. 46, pp. 2721-2724.
39. Smith, D. W., December 13, 1982, ”Runaway Reactions and Thermal Explosion”, Chem.Eng., pp. 79.
40. Smith, D. W., May 14, 1984, ”Assessing the Hazards of Runaway Reactions”, Chemical Engineering, pp. 54.Lee, P. R., 1969, J. Appl. Chem., Vol. 19, pp. 345-351.
41. Stull, 1977, “Fundamentals of Fire and Explosion,” AIChE Monograph Series No. 10, New York, American Institute of Chemical Engineers, Vol. 73, pp. 21-22.
42. Townsend, D. I., and Tou, J. C., 1980, “Thermal Hazard Evaluation by an Accelerating Rate Calorimeter”, Thermochimica Acta, Vol. 37, pp. 1-30.
43. Wagle, U. D. et al., Mar 1978, “Organic Peroxide Decomposition Characteristics” Combustion and Flame v 3 Vol.3, pp. 62-69.
44. Wang, Y. W., Shu, C. M., Duh, Y. S. and Kao, C. S., 2001, “Thermal Runaway Hazards of Cumene Hydroperoxide with Contaminants”, Ind. Eng. Chem. Res. Vol. 4, pp. 1125-1132.